Waterproofing of cement and allied compositions



Patented May 25, 1954 WATERPROOFING OF CEMENT AND ALLIED COMPOSITIONS Troy, and Frederick G.

Daniel W. Kennedy,

Weigand, Ballston Lake, N. Y

., assignors to General Electric Company, a. corporation of New York No Drawing. Application February 8, 1951, Serial No. 210,092

6 Claims.

This invention is concerned with the waterproofing of cement and other allied compositions, such as concrete, etc. More particularly, the invention relates to a cczzient waterproofing composition comprising by Weight 1) from 50 to 95 per cent of an oil-modified alkyd resin and (2) from 5 to 50 per cent of an organo-polysiloxane resin cold-blendable and compatible with the alkyd resin.

especially during the stage when the concrete is first poured or formed.

Other objects of the invention will become more apparent from the following description of the invention.

Cement, concrete, and similar compositions are used extensively, especially in the building and highway arts. In the former case, cement or concrete blocks are used in building houses, and other architectural structures. It has often been desired to coat the outside of the concrete blocks so as to minimize the entrance of water from the atmosphere in order to preserve the concrete blocks and also in order to avoid undesirable dampness which might develop in the pores of the concrete blocks because of the entrance of water. This waterproofing is often desirable as undercoating for architectural paints and finishes. In road-building, when concrete is first poured it is in a rather fluid condition and contains a relatively large proportion of water. This water will evaporate in time to give the customary hard surface. In order to prevent too rapid an evaporation of water from the surface of the freshly poured concrete, various means have been employed to eifect a slowdown of water evolution as, for example, by putting straw or clcth over the surface of the freshly poured concrete. The slower the evaporation of the water from the concrete surface, the more the concrete has a change to knit and form a harder surface than is the case when the water evolves too fast.

Many coating compositions have been evolved for waterproofing cement and allied materials (for brevity, the word cement will be used to include cement, concrete, and similar compositions) but in general no one material has been completely satisfactory, although they have been able to cut down somewhat the entrance of water into concrete and to prevent excessive water evolution from freshly poured concrete. We have now discovered unexpectedly that a combination of specific non-interacted resins when applied in the form of a relatively dilute solution to concrete greatly improves the ability of the concrete to resist the entrance of water and also advantageously decreases the rate of evolution of Water from concrete, e. g., from freshly poured or freshly formed concrete surfaces. More particularly, we have found that the combination of an oilmodified alkyd resin and a compatible and coldblendable (i. e., in solution) organopolysiloxane resin in the form of a dilute solution is eminently suitable for the purposes described above. It was entirely unexpected and in no way could have been predicted that the combination of these two resins would be so useful for waterproofing cement since the individual resins by themselves were markedly inferior for that purpose to the combination of resins.

The organopolysiloxane resin which We have found to be outstanding'for the above purpose is one more particularly described and claimed in the copending application of Welsh and Holdstock, Serial No. 210,094, filed concurrently herewith and assigned to the same assignee as the present invention, now U. S. Patent 2,661,348 issued December 1, 1953. This resin is prepared by hydrolyzing an organohalogenosilane or mixture of organohalogenosilanes with a hydrolysis medium comprising water and a halogenated organic liquid which is a solvent for the organohalogenosilane or mixture of organohalogenosilanes and the formed organopolysiloxane, the said solvent having a specific gravity above 1.1 (preferably above 1.2) and a boiling point below C., and being inert to the formed hydrogen halide, to the aforesaid organohalogenosilane, and the formed organopolysiloxane. In one of the embodiments of the invention described and claimed by Welsh et al., the organohalogenosilane compositon is formed into a solution with the halogenated organic liquid and this solution is thenadded to the hydrolyzing water. The hydrolyzable organohalogenosilane or mixture of organohalogenosilanes may be any one of those well known in the art and may comprise, for example, methylchlorosilanes or phenylchlorosilanes or mixtures of phenylchlorosilanes and methylchlorosilanes (or phenyl methylchlorosilanes) in various ratios, preferably in a ratio wherein the total number of organic groups to silicon atoms ranges from about 1 to 2 and preferably within a narrower-range of from about 1.2 to 1.8. The above-mentioned Welsh et al. application gives many examples of organohalogenosilanecompositions which can be employed as well as various hydrolyzing media including various halogenated organic liquids which can be used as solvents for the organohalogenosilane and, of course, for the formed organopolysiloxane. In view of the more than adequate disclosures in the Welsh et a1. application, which by reference is made part of the present application, no further description of the process therein resin in a suitable solvent for both these resins disclosed and claimedwill be given hereinas, for example, xylene, toluene, benzene;:mineral It is to be understood that other organopolyspirits, petroleum spirits, butanol', or mixtures of siloxanes cold-blendahle and compatible witf'i any one or more of these solvents which are the oil-modified alkyd resin may also be emsatisfactory solvents for the resins. The type of ployed without departing from the scope of the solvent employed is not critical and any one of invention. Among such organopolysiloxahes the many well known in the art may be used. resins which may be mentionedare, e. g., methyl; Resin solids. contents ranging from 1 to per ethyl, propyl, butyl, phenyl, tol'yl, cyclohexyl, cent, by weight, of the total solution are adbenzyl, vinyl, allyl polysiloxanes, mixed organom vantageously employed. polysiloxanes, for instance, methyl and phenyl, In order to accelerate the conversion of both ethyl and phenyl, allyl and.metl1 1;ivinyl* and the'oilemodified alkyd resin and the organopolymethyl and phenyl, allyl and methyl and phenyl; siloxane resin to the substantially infusible and etc., polysiloxanes in which the organic groups." insolublestate after application to the cement in the organopolysiloxanes are attached to the is surface, small amounts of paint driers which have silicon. atoms. thereof. bycarbonesilicon linkages, been known to be cure accelerators for both these and. .where both methyl and phenyl. groups are resins are advantageously incorporated. inthe in the polysiloxane. molecule, thev methyl and coating composition. In this connectionattenphenyl groups may be onthe. same or different tion is directed to Welsh Patent 2,449,572 issued silicon atoms. 3,) September 21, 1948,. and assigned to thesame The oil-modified alkyd resins which. can be assignee as the present invention. This .latter employed in the practice. of. thepresent invention patent discloses a multitudeof drierswhich have include the resinous condensation products rebeen found suitable for the purpose withrespect sulting from the reaction. of. one or more polyto both the oil-modified alkyd resin and the hydric alcohols with one or more polycarboxylic organopolysiloxane resin... The amount of acacids or anhydrides. using as the. oily modifying celerator used may, of course, bevaried within ingredient those normally employed in the prepwide limits but generally we have foundthatthe aration. of oil-modified alkyd resins. Examples accelerator may comprise, for example, from of polyhydric alcohols. (dihydric, trihydric, etc.) about 0.01 to as high. as 3 to 5 .per cent, based which. may be used in making the oil-modified on the total weightof the resin solids innthe alkyd resin are, for. instance, ethylene glycol, diwaterproofing composition. We have found that ethylene glycol, propylene glycol, dipropylene thev naphthenates. oflead, cobalt and-calcium. glycol, glycerine, pentaerythritol, sorbitol, etc. and the octoates of zincandother metals are Monohydric alcohols, e., g.,. those boiling above especially suitable for the purpose. 150 C. such. as the alkyl. ethers of diethylene 55 It has beenfound'that: optimumresults from glycol, e. g., methyl ether of diethylene glycol, the mixture of the organopolysiloxane resin and etc.; butyl ether of diethylene. glycol, may also the oil-modified. alkyd. resin arerealizedwhen be used to modify the properties of the oilthe organopolysiloxane.resin-comprisesa certam modified alkyd resin. per cent of the total mixture-of the lattenand Among the polycarboxylic. acids which. may be 40 the oil-modified alkyd resin. On aweight basis employed in making the. oil-modified alkyd resin and considering only the resin solids content-oi are, for example, the saturated aliphatic or arothe waterproofing agent, it has been found that matic polyearboxylicacids, especially the dicarsmall amounts of the organopolysiloxane resin boxylic acids, among which may be-mentioned, as low as, for example, 5 per cent, by weight, of

for example, oxalic, malonic, succinic, adipic, trithe mixture of resins, exercise a markedimprovec y p t c, isophthalic, terephthalic, mentin the waterproofing-properties ofthe comdiphenic, naphthalic, etc., acids (anhydrides may position. In general, the organopolysiloxane resb d Without departing from the SCODBOf the in should comprise froinabout 5 to per cent,

invention). If desired, monocarboxylicacids, for preferably from b t, 10 m 35 er cent, of the eXamp1e,benZ0iC.a0id, y 24150 be used to modify total weight of the organopolysiloxane resin and the p p the oil-modified alkyd-resin; Amounts of organo- The modifying oily ed e employedslin polysiloxane resin in'excess of '75 per cent cause mak ng th Oil-modified alkyd resins are plief'efa decrease in the effectiveness of the mixture b y those selected from the classyconsistine of of resins to adequately waterproof the cement. n -d yi Oils Semi-drying Oils, y It was also found that only organopolysiloxane fatty O l Oil and miXturet thereof, resins compatible (i. e., those which when mixed all. the foregoing being derived, for e a p with the oil-modified alkyd resin gave in solueith r ro Vegetable animal 501111188 D tion a homogeneous mixture andwhen deposited dined sy y, c- Among the. m0difylng as a cured-filmirom whichthe solvent has-been 011s (1n he aw, he blown State). Whlch volatilized. will have-a clearqappearancel with ayb u are, for example, linseed 011,.rapethe oil-modified alkyd resins could be used in seed, cottonseed;.China+wood oil, castor oil (int practice of t invention and'ithat incom eluding raw castor oil), dehydrated castor oil, patible t commonly soluble organopolysiloxane soya bean oil, oiticica oil, coconut oil fatty acids, resins t t commomy 501111318 with the 11.. fatty acid. glycerides, etc. Additional examples. modified alkyd resins) gave t i uy poorer 0f po y yf a1Q0h01$, polycaltloxylic acids, and waterproofing properties and characteristics as Oily modlfying mgfedlents Whlch may be compared to the particular organopolysiloxane ployedare found in the Ham Patent 2,491,811 resin prepared by method described. d issued December 20, and assigned. to the claimed the aforementioned Welsh et. a1 pat.. same assignee as the: present invention. We m; pr to u Oil-modified e y -p Although the solids content of the waterproofresins which are'wellknownin the art. ing composition (that is, the solution of resins) In making thewaterproofing composition in maybe varied within fairly wide limits; neverusable form,- it: is desirable to dissolve the oiltlieless wehave' found it eminently suitable that modified alkyd resin and the organopolysiloxane' .75 the solids'contentthereoi rangefrom about 1 in the following examples measured 6 x 12 x 1 inches. Each concrete slab was allowed to age at room temperature for two lowed to air-dry at room temperature for 48 hours. At the end of that time, they were completely immersed in water with the results shown below.

EXAMPLE 1 An organopolysiloxane resin was prepared in claimed in the aforementioned Welsh et a1 application as follows. A blend was prepared by mixing together mol per cent methyltrichlorosilane, mol per cent phenyltrichlorosilane, 20 mol per cent dimethyldichlorosilane, and 20 mol per cent diphenyldichlorosilane. 500 grams of this blend was mixed with 750 grams of trichloroethylene to form a homogeneous solution and this solution was then added to a well-stirred mass of 2000 grams of water at 35 C. The solvent-silane blend was added slowly through an inlet tube which dipped well below the surface of the water. Total addition time was 22 minutes during which time the temperature of the hydrolysis mixture rose to 72 C. Stirring was continued for another 5 minutes and thereafter the mixture was allowed to separate. The lower trichloroethylene layer of the resin was separated and stripped of most of the solvent by heating to a pot temperature of 150 C. At this point 130 grams of xylene was added to the resin and the resulting solution was heated to gentle reflux for 1 hour. After filtering, the solution was adjusted to per cent resin solids by adding the required amount of xylene.

A spraying solution was then prepared by mixing together 48 parts of a linseed oil fatty acid modified glyceryl-phthalate alkyd resin in a petroleum spirits solvent (50 per cent solids), 10

'siloxane resin alone (containing a cure accelerator) and the. above described oil-modified alkyd 'resin (containing a drier specifically a mixture of 6 metal naphthenates). The following table shows the per cent gain of water over the original weight of the concrete slab.

Table 1 Percent Percent Percent Resin Gain 8 Gain 24 Gain 48 Hours Hours Hours M None-Control 7. 57 7. 6 7. 6 Oil-modified alkyd alone 6. 35 8. 56 8. 77 Organopolysiloxane resin alone 6. 3 9. 2 9. 35 A] yd-organopolysiloxane combination l. 95 3. 73 4. 93

The foregoing table illustrates clearly the unexpected and unpredictable result that the combination of the organopolysiloxane resin and the oil-modified alkyd resin is materially better than each of the resins individually when employed for waterproofing cement.

EXAMPLE 2 In this example the oil-modified alkyd resin and Example 1. The sprayed panels were then airdried 48 hours at room temperature and immersed in water with the results shown below. Table 2 describes the proportions of oil-modified alkyd resin and organo-polysiloxane resin. Table 3 discloses the results of the immersion tests in which the sprayed concrete panels were immersed in water for the time designated in Table 3.

Table 2 Percent s ii/ 52m by Weight Sample No. Oil-Modir 5" fied Alkyd 23,5 Resin Resin Table 3 RM Percent Weight Increase Sample No.

2 Hours 4 Hours 6 Hours Control (No coating) 9. 8 9. 8 9. 8 A 6.1 7. 6 8. 2 B 6.1 7. 5 7. 9 C... 4. 7 6.0 6.6 D 3. 6 4. 9 5. 5

EXAMPLE 3 This example illustrates the ability of the organo-polysiloxane-alkyd resin combination to that they hadvabsorbed a maximum amountof waten. The panels wereremoved from water and allowed to dry at room temperature:whileweights of the panels were taken at intervals. The per cent figures in Table 4 below indicate the amount oi'water still remaining in the panels. The resins used comprised the same three employed in Ex- 1 Each resin solution comprised a 5' percent solids concentration. clearly that not only can our claimed compositions be used effectively tominimize the moisture absorption of concrete but'al'sothey can be applied to concrete surfaces orthe purpose of decreasing the rate of volatilization of the moisture contained therein and thereby give improved concrete surfaces and mproved-concrete products.

EXAMPLE 4 This examplershows the'effect oftreating stucco panelswithaour claimed composition and thereafter-applying thereto two coats of paint after which the panels were placed on exposure to the elements as, e. g., sun, rain, sleet, etc, for two months and thereafter the panels were removed and the water absorption tests started using the same tests as described in Example 1. The organopolysiloxane resin solution and the organopolysiloxane-oil-modified alkyd resin solution combination used in this example are identical with those described above in Example 1. In'each case after application of the under waterproofing coating, the successive two top coats were applied one on top of the other, permitting the first top coat to dry before the second coat was applied. Inone case a regular outside white oil-base paint comprising titanium was used as one pair of top coats, while in another case, a rubber-base cement comprising chlorinated rubber in combination with linseed oil was used as the other pain of top coatings. The followingTa-ble 5 shows the results of these waterimmersion tests after the respective panels were subjected to the tests described above.

Table 5 Resin Top Coat Oil-baselaint:

Control 1. 4 Organopolysilorane Un c it 0.4 1.2 1.4 2.0 Alkyd resinnndercoat 0. 4 l. 3 1.7 2.1 Organopolyslloxane-alkyd underocat 0.1 0.7 0. 9 l. 3 :T i ubbcr-base Paint:

Control 1.1 2.6 3.1 3 5 Organopolysiloxane underc l. l 2. 3. 2' 3. 6 Alkyd resin undercoat. 0.2 1.0 l. 4 l. 7 Organopolysiloxane-nlkyd undercoat; 0. a 0. a l 1. 0 1. 4

N0 waterproofingzbcneathitop costs:

dioxide in a linseed oil base various concrete ZItt. wasonoticed: that; when: the: mixture. of. the organopolysiloxane;v resinrand. the oil-modified alkyd resin was. used as: arwaterproofing agent on stucco,v either with: or-wit-hout' the 'topucoats' of paints, checking. ofi thew stucco surface: was either-greatly reduced 'orrcomple'tely eliminated. 'Ilhis isianunusualzproperty since the-undercoats of. the-alkyd resin alone or the organopolysiloxe ane resin; alone; eitherrha'dr very: little effect. on or failed completely in the elimination of checking; Ilhe: stucco: samples which contained no undercoating atallzwere badly checked.

It. will,, of course; beea-pparent to those: skilled in: the art that other. organopolysiloxanespre pared: accordance: Wl'bhl the descriptions: outlined in the raiorementionedzwelsh and Holdstock application, many examples of which are given in..the latter 'application; as well as many other types of: oil-modified alkyd-resins previously -dee scribed: may; be employed iniplace: of; the-ones used; inithei foregoing examples In addition; the proportion of ingredients may be varied within the more: desirable limitsmentioned-above; and other drying; or curing agents may be? employed in 1312.08J0f the naphthanates orvcctoates;-men tioned in the preceding examples. Various-types of solvents can be substituted for those used above but caution should be exercised in that the choice of solvents does not. resultin throwing out one of the two resinous components" comprising the waterproofing material.

As will be apparent from the preceding; 'description of the invention; our" compositions of matter' are eminently. suitable for' protecting surfaces, and improving their water-resistance: lni'addi'tion; our'claime'd'compositions of" matter may "also be used in applications requiring a minimum of loss ofwaterfrom freshly constructed concrete surfaces in order to permit the concrete tohardenat'a'more desirable rate which in' many-respects is controlled by the rat'e'of water-evolved fromthe-concrete surface:

Whatwe claim asnewand desire to secure by Letters Patent of the-UnitedStates is:-

11 cement waterproofing composition com.- prisin'g-a 1 to IOper-cent solidsorganic solution of a compatible; cold-bl'endablemixture offnoninteracted ingredientscomprising (-1). an' organepolysil'oxane resin in which the organic groups areselected from theclass consisting "of methyl, ethyl; 'ph'enyl radicals',.andmixtures'of such radicals attached 'to' silicon by carbon-sili'corrlinkages and" obtained by hydrolyzing an organ'o "chlorosilane designed to giv the above-mentioned organopolysiloxane-witha mixture orinjgredient'sconsistin essentiallypt (a) water and (Iiia. liquid'chlorinated hydrocarbon which. is a solvent for both theorgano chl'orosilane andJthe formed--organopolysiloxane, said solvent having a specific gravityabove 1:1 and a boilin'gpoint below 175 C. and being inert to any formed hydrogen chloride, tothe aforesaid organo'chlorosilanerand to theorganopolysil'oxane, and (2t an oil-modified alkyd resin, thesaid organopolysiloxane' resin comprising, byweight; from 10 to 50-per-cent of the total weight of the latter and'the oil-modifled alkyd resin;

2': A cement waterproofing composition comprising a; I to-lOl-per cent solids organic solution of a compatible, cold-blendable mixture of noninteracted ingredientscomprising (1)" a methyl phenyl polysiloxane-resin obtained by 'hydrolyzing a' mixture of organochlorcsilanescomprising a methylchlorosilane-and-a'phenylchlorosilane'witn a mixture of'ingredients eonsisting-essentially-ot (a) water and (b) a liquid chlorinated hydrocarbon which is a solvent for both the organochlorosilane and the formed organopolysiloxane, said solvent having a specific gravity above 1.1 and a boiling point below 175 C. and being inert to any formed hydrogen chloride, to the aforesaid organochlorosilane and to the organopolysiloxane, and (2) an oil-modified alkyd resin, the aforesaid methyl phenylpolysiloxane comprising from to 50 per cent of the total Weight of the latter and the oil-modified alkyd resin.

3. A cement waterproofing composition comprising a 1 to 10 per cent solids organic solution of a compatible, cold-blendable mixture of noninteracted ingredients comprising (1) a methylpolysiloxane obtained by hydrolyzing a mixture of methylchlorosilanes comprising methyltrichlorosilane and dimethyldichlorosilane with a mixture of ingredients consisting essentially of (a) water and (b) a liquid chlorinated hydrocarbon which is a solvent for both the methylchlorosilanes and the formed methylpolysiloxane, said solvent having a specific gravity above 1.1 and a boiling point below 175 0., and being inert to any formed hydrogen chloride, to the aforesaid methylchlorosilanes and to the methylpolysiloxane, and (2) an oil-modified alkyd resin, the said methylpolysiloxane resin comprising, by weight, from 10 to 50 per cent of the total weight of the latter and the oil-modified alkyd resin.

4. A waterproofing composition for cement comprising a 1 to 10 per cent solids organic solution of a compatible, cold-blendable mixture of non-interacted ingredients comprising 1) a methyl phenylpolysiloxane resin obtained by hydrolyzing a mixture of organochlorosilanes comprising methyltrichlorosilane, phenyltrichlorosilane, and dimethyldichlorosilane with a mixture of ingredients consisting essentially of (a) water and (b) trichloroethylene and (2) a linseed oil-modified glyceryl-phthalate alkyd resin, the aforesaid methyl phenylpolysiloxane comprising from 10 to 50 per cent of the total weight of the latter and the oil-modified alkyd resin.

5. A cement waterproofing composition comprising -a 1 to 10 per cent solids organic solution of a compatible, cold-blendable mixture of non-interacted ingredients comprising (1) a methyl phenylpolysiloxane resin obtained by hydrolyzing a mixture of methylchlorosilanes comprising inethyltrichlorosilane and dimethyldichlorosilane in a hydrolysis medium consisting essentially of (a) water and (b) a liquid chlorinated hydrocarbon which is a solvent for both the organochlorosilanes and formed methyl phenylpolysiloxane, said solvent having a specific ravity above 1.1 and a boiling point below C. and being inert to any formed hydrogen chloride, to the aforesaid organochlorosilanes, and to the formed methylpolysiloxane, and (2) an oilmodified alkyd resin comprising a linseed oilmodified glyceryl-phthalate alkyd resin, the said methylpolysiloxane comprising, by weight, from 19 to 50 per cent of the total weight of the latter and the oil-modified glyceryl-phthalate alkyd resin.

6. A cement waterproofing composition comprising a 1 to 10 per cent solids organic solution of a compatible, cold-blendable mixture of noninteracted ingredients comprising (1) an organopolysiloxane resin in which the organic groups are selected from the class consisting of methyl, ethyl, phenyl radicals, and mixtures of such radicals attached to silicon by carbon-silicon linkages and obtained by hydrolyzing a mixture of organochlorosilanes designed to give the abovementioned organopolysiloxane in a hydrolysis medium consisting essentially of (a) water and b) trichloroethylene, and (2) a linseed oilmodified glyceryl-phthalate alkyd resin, the organopolysiloxane resin comprising, by weight, from 10 to 50 per cent of the total weight of the latter and the oil-modified alkyd resin.

References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Paint, Oil 8; Chemical Review, Nov. 11, 1948, pages 49-51. 

1. A CEMENT WATERPROOFING COMPOSITION COMPRISING A 1 TO 10 PER CENT SOLIDS ORGANIC SOLUTION OF A COMPATIBLE, COLD-BLENDABLE MIXTURE OF NONINTERACTED INGREDIENTS COMPRISING (1) AN ORGANOPOLYSILOXANE RESIN IN WHICH THE ORGANIC GROUPS ARE SELECTED FROM THE CLASS CONSISTING OF METHYL, ETHYL, PHENYL RADICALS, AND MIXTURES OF SUCH RADICALS ATTACHED TO SILICON BY CARBON-SILICON LINKAGES AND OBTAINED BY HYDROLYZING AN ORGANOCHLOROSILANE DESIGNED TO GIVE THE ABOVE-MENTIONED ORGANOPOLYSILOXANE WITH A MIXTURE OF INGREDIENTS CONSISTING ESSENTIALLY OF (A) WATER AND (B) A LIQUID CHLORINATED HYDROCARBON WHICH IS A SOLVENT FOR BOTH THE ORGANOCHLOROSILANE AND THE FORMED ORGANOPOLYSILOXANE, SAID SOLVENT HAVING A SPECIFIC GRAVITY ABOVE 1.1 AND A BOILING POINT BELOW 175* C. AND BEING INERT TO ANY FORMED HYDROGEN CHLORIDE, TO THE AFORESAID ORGANOCHLOROSILANE AND TO THE ORGANOPOLYSILOXANE, AND (2) AN OIL-MODIFIED ALKYD RESIN, THE SAID ORGANOPOLYSILOXANE RESIN COMPRISING BY WEIGHT, FROM 10 TO 50 PER CENT OF THE TOTAL WEIGHT OF THE LATTER AND THE OIL-MODIFIED ALKYD RESIN 